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FAMEs with a High Iodine Number - Literature Review

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Appendix 1: Fatty Acid Methyl Esters with a High Iodine Number Literature Review
Heinrich Prankl BLT Wieselburg A-3250 Wieselburg, Austria The effect of unsaturated acids in fatty acid methyl esters being used as biodiesel in engines was investigated in several projects. The following reports are reviewed: [1] WRGETTER, M., et.al.: Pilotprojekt Biodiesel. Forschungsberichte der Bundesanstalt fr Landtechnik, Wieselburg. Heft 25 und 26. A-3250 Wieselburg (1991) PRANKL, H., WRGETTER, M.: Influence of the Iodine Number of Biodiesel to the Engine Performance. Proceedings of the 'International Conference on Standardization and Analysis of Biodiesel', 6-7 Nov 1995, Vienna. ISBN 3 9014 5701 1. PRANKL, H., WRGETTER, M.: Influence of the Iodine Number of Biodiesel to the Engine Performance. Proceedings of the ASAE Conference 'Liquid Fuels and Industrial Products from Renewable Resources', 15-17 Sep 1996, Nashville, Tennessee. ISBN 0-929355-79-2. BLACKBURN, J.H., et.al.: Performance of Lubricating Oils in Vegetable Oil Ester-Fuelled Diesel Engines. SAE Technical Papers 831355 (1983). SIEKMANN, R.W., et.al.: The Influence of Lubricant Contamination by Methylesters of Plant Oils on Oxidation Stability an Life. Proceedings of the International Conference on Plant and Vegetable Oils as Fuels. ASAE (1982). BAUMANN, W., HUBMANN, A.: Anforderungen an das Motorl bei Einsatz von Rapslmethylester. Symposium RAPSMETHYLESTER - Kraftstoff und Rohstoff. Tagungsband. 30.9.-1.10.1992. Wien (1992). ISBN 3 900554 11 0. KORUS, R.A., MOUSETIS, T.L.: Polymerization of Safflower and Rapeseed Oils. JAOCS, vol. 61, no. 3 (1984). PRANKL, H., et.al.: Technical Performance of Vegetable Oil Methyl Esters with a High Iodine Number (e.g. Sunflower Oil Methyl Ester, Camelina Oil Methyl Ester). Interim Report of ALTENER XVII/4.1030/Z/96-013. Federal I stitute of n Agricultural Engineering, Austria (1997). PRANKL, H., WRGETTER, M.: Technical Performance of Vegetable Oil Methyl Esters With a High Iodine Number. Fourth Biomass Conference of the Americas, Oakland, California, USA (29 Aug - 2 Sep 1999).

[2]

[3]

[4] [5]

[6]

[7] [8]

[9]

NTB net / May 1999

H. Prankl / BLT Wieselburg

FAMEs with a High Iodine Number - Literature Review

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WRGETTER, BLT Wieselburg [1]:

In the project a Steyr WD411 test engine (4 cylinders, 60 kW, 2200 rev/min, 3456 cm) was operated on the test bench during 1000 hours. Rape seed oil methyl ester from a 00-rape used as test fuel and a Castrol/Deusol 30 (SAE 30/MIL C) was used as engine oil. The test was carried out without oil change. Oil samples were analysed each 50 hours. At 300 hours the content of fuel in the engine oil attained 17% but decreased again to 10%. After a drop until 250 hours the viscosity raised again. Polymerisation reactions of polyunsaturated fatty acids in the engine oil are supposed.

Viscosity and content of rapeseed oil methyl ester (RME) in the engine oil

Trend of the viscosity during the 1000 hours test run

NTB net / May 1999

H. Prankl / BLT Wieselburg

FAMEs with a High Iodine Number - Literature Review

Page 3

PRANKL, WRGETTER, BLT Wieselburg [2], [3]: Long term tests were carried out on a HATZ-single cylinder engine over 250 hours with 5 several fuels. The fuels were produced out of blends between high oleic sunflower oil methyl ester and linseed oil methyl ester: Test fuel VK1 VK2 VK3 VK4 VK5 high oleic sunflower oil methyl ester 100% 75% 50% 25% 0% linseed oil methyl ester 0% 25% 50% 75% 100% iodine number 100 120 140 160 180

The engine oil was pre-mixed with 10% of each test fuel before start. The content of ester decreased during the run down to <2% while the viscosity increased. There couldnt be seen significant differences until an iodine number of 160. The inspection of the engine after each test showed a high cleanness and no differences in the formation of deposits on cylinders, combustion chambers, valves and injectors. Increasing deposits with increasing iodine number could be observed at piston rings on the bottom of the 2nd ring groove.
Increase of Viscosity vs. Iodine Number
0,80 Serie a Serie b 0,60 Mittelwert b

Average increas of viscosity 100C in 10 h [mm/s]

0,70

0,50

0,40

0,30

0,20 100 110 120 130 140 Iodine number 150 160 170 180

Dependence of increase of viscosity (average during 125 hours) and iodine number

35

30

25

Rating Factor

20

15

10

0 100 120 140 Iodine Number 160 180

Piston rating after a 250 hours test (Source Mercedes Benz)

NTB net / May 1999

H. Prankl / BLT Wieselburg

FAMEs with a High Iodine Number - Literature Review

Page 4

BLACKBURN, J.H., et.al., Shell Brasil S.A. [4] A series of engine dynamometer tests were carried out with soya oil ethyl ester and 6 different engine lubricants. A 4 cylinder direct injection diesel engine was used with a rated power of 61 kW at 2800 rpm. The tests consisted of a series of 10 hours running per day at full rated load/speed. Fatty acid profile of the fuel: Ethyl Palmitate (C16:0): Ethyl Stearate (C18:0): Ethyl Oleate (C18:1): 7% 3% 22% Ethyl Linolate (C18:2): Ethyl Linoleate (C18:3): Total glycerides 58% 10% 0,5%

In each case the lubricant became contaminated by unburned fuel up to 15-20% after 40 hours. A reduction of the kinematic viscosity was recorded. Afterwards the viscosity increased again. The test was terminated after lubricant breakdown was encountered (total loss of dispersancy). The engine oil separated in two phases. The failure of the lubricant is due to the rapid oxidation of some of the fatty acid ester components which probably led to polymerisation.

NTB net / May 1999

H. Prankl / BLT Wieselburg

FAMEs with a High Iodine Number - Literature Review

Page 5

SIEKMAN, R.W., et.al., Volkswagen do Brasil S.A. [5] Mixtures of several methyl esters (from soybean oil, iodine number 128, and babassu oil, IN 17) and lubricating oil were used for studies in laboratory and engine tests. The lab tests (using a McCoull apparatus at 150C and 170C) have shown that the amount of double bounds introduced is significant in increasing viscosity and reducing TBN. GC analysis of extracted ester show degradation mainly in fatty acids with conjugated double bonds. Bench tests and mixed-driving tests gave similar results.

BAUMANN, W., HUBMANN, A., OMV Austria [6]: Long term tests were carried out with 2 stationary engines (Steyr WD 614S and Caterpillar D 398) and rapeseedoil methyl ester as fuel. The content of unburned fuel in the engine oil increased to 8 and 10% during the test period of 1000 hours. While the Caterpillar engine showed a decrease in the engine oil viscosity until the end of the test, the viscosity of the Steyr engine climbed up again after 600 hours. It is supposed that RME showed reactions of condensation or polymerisation and was degraded to products with a higher viscosity.

Content of rapeseed oil methyl ester during the test

NTB net / May 1999

H. Prankl / BLT Wieselburg

FAMEs with a High Iodine Number - Literature Review

Page 6

Engine oil viscosity during the test PRANKL, WRGETTER, BLT Wieselburg [8], [9]: Long term tests were carried out on the test bench with rape seed oil methyl ester, sunflower oil methyl ester and camelina oil methyl ester with an iodine number of 107 to 150. The oil viscosity was observed and the engine parts were inspected after each run. A correlation could be found between the increase of the engine oil viscosity and the iodine number. Additionally the increase of viscosity depends on the temperature of the engine oil.
14,5 14,0 13,5
CME

Viscosity 100C [mm/s]

13,0 12,5 12,0 11,5 11,0 10,5 10,0 0 32 64 96 128 160 192 224 256
RME SME

Running Time [h]

A fleet test with 9 vehicles and 1 stationary engine was carried out over a period of 1 to 3 engine oil drain intervals. Camelina oil methyl ester was used with an iodine number of 150 and a content of 37% linolenic acid (C18:3). The engines were dismantled before and after the tests. No unusual deposits could be found in the cylinder liner, the combustion chamber, the injector and the valves.

Engine oil viscosity vs. running time The experiences have shown that it is possible to operate an engine with a methyl ester containing more than 30% of poly-unsaturated acids. Further investigations are necessary especially in the interaction between methyl ester fuel and engine oil.

NTB net / May 1999

H. Prankl / BLT Wieselburg

FAMEs with a High Iodine Number - Literature Review

Page 7

KORUS, R.A., et.al., Univ. of Idaho, Moscow, USA [7] Rates of polymerisation of safflower and rapeseed oil were measured in the air and under vacuum. Oxidative polymerisation occurs by the interaction of double bonds and oxygen to form peroxides. Thermal polymerisation is favored by the presence of conjugated double bonds and is negligible at temperatures below 250C. Rates of thermal polymerisation showed a stronger dependence on the degree of unsaturation than oxidative polymerisation.

Summary and conclusions The use of methyl esters in diesel engines might cause engine oil dilution by the fuel. A high content of unsaturated acids in the esters (expressed by a high iodine number) increases the danger of polymerisation in the engine oil. The engine oil dilution leads to a decrease of viscosity. In several publications a sudden increase could be found after a time. It is supposed that the oil breakdown is related to fuel dilution followed by oxidation and polymerisation of unsaturated fuel constituents. On the other hand a lot of tests have shown that it is possible to use methyl esters with a high iodine number in engines. It is supposed that the iodine number is not well suited to describe the effects of methyl ester in the engine. One value can be attained by using several grades of unsaturated acids. That is why an additional parameter was included in ON C1191, Austrians standard for FAME: The content of linolenic acid (C18:3) was limited to 15%.

NTB net / May 1999

H. Prankl / BLT Wieselburg

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